CN103709373A - Hyperbranched polyurethane acrylate UV light-cured resin and preparation method thereof - Google Patents
Hyperbranched polyurethane acrylate UV light-cured resin and preparation method thereof Download PDFInfo
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- CN103709373A CN103709373A CN201310667832.4A CN201310667832A CN103709373A CN 103709373 A CN103709373 A CN 103709373A CN 201310667832 A CN201310667832 A CN 201310667832A CN 103709373 A CN103709373 A CN 103709373A
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- polyurethane acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/833—Chemically modified polymers by nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The invention provides a hyperbranched polyurethane acrylate UV light-cured resin with a novel structure, and relates to an application of the resin. The resin has the following structure as shown in the specification. A preparation method of the resin comprises the steps: firstly carrying out a reaction of a diisocyanate monomer with a dihydric alcohol, and then carrying out a reaction with a single amino polyhydroxy monomer to prepare an ABn reaction intermediate having end groups with an isocyanate group and a plurality of hydroxyl groups; allowing the ABn reaction intermediate to undergo a self-polycondensation reaction, and preparing hyperbranched polyurethane (HPU-Xm) containing terminal hydroxyl groups; carrying out a reaction of the diisocyanate monomer with hydroxyalkyl acrylate, and thus obtaining a reaction intermediate C containing an isocyanate terminal group and an acrylic double bond terminal group; and carrying out a reaction of the reaction intermediate C with HPU-Xm, and obtaining the UV light curable hyperbranched polyurethane acrylate resin product averagely containing 2-32 double bonds. The product contains more terminal double bonds, can perform fast light curing, is suitably used as UV curable coatings, adhesives, rheological processing additives, active compounds and the like, and has wide application prospects.
Description
Technical field
The invention belongs to light-cured resin technical field, particularly relate to the preparation method of ultra-branched polyurethane acrylate UV light-cured resin.
Background technology
Ultraviolet (UV) curing technology is the new technique of an energy-conservation and environmental protection.In ultraviolet-curable materials, do not contain or only contain a small amount of solvent, the energy used of ultra-violet curing effect is simultaneously electric energy, therefore ultra-violet curing is described as " green technology ".The patent that nineteen forty-six American I nmont company has applied for first uv curing ink, nineteen sixty-eight, Germany Bayer company developed first-generation ultra-violet curing woodwork coating, and ultra-violet curing technology obtains and develops rapidly in the world.
As far back as nineteen fifty-two, Flory has just proposed to prepare highly branched polymkeric substance by polyfunctional monomer; But in the past few decades,, highly branched polymkeric substance does not attract much attention, and is mainly the research to dendritic polymer.Until 20th century the mid-80, the people such as the Kim of E.I.Du Pont Company have on purpose synthesized a kind of hyperbranched polymer, and applied for first (U.S.Pat. 4857630 of the patent about this respect, 1987.), and announced this achievement in the whole America chemistry meeting of holding at Los Angeles,U.S for 1988, from then on, the structure of hyperbranched polymer uniqueness and performance cause various countries scientist's interest, become the focus of research.
Hyperbranched polymer is the highly branched macromole with three-dimensional dimension dendritic structure.Compare with dendritic macromole, the degree of branching of hyperbranched polymer is little, and molecular weight distribution is wide, and geometrical isomer is many, and its geometric shape do not have dendritic macromole rule, and molecular structure exists defect.But advantages such as it is low that it has viscosity, and solvability is high, good film-forming property, and synthesis technique is simple, cost is low, is conducive to scale operation, so hyperbranched polymer has important theoretical significance, and has broad application prospects.
Urethane has purposes widely at multiple fields such as coating, tackiness agent, rubber, plastics, fibers.The existing relevant report of preparation of super branched polyurethane.Macromolecules, Vol.36,613-620(2003), Chinese patent CN 1385450(2002), Chinese patent CN 1385451(2002) Chinese patent CN1791621(2006), Chinese patent CN1966544(2007), Chinese patent CN101074278(2007) use monomer and di-isocyanate reaction containing tertiary N atom and a plurality of hydroxyls to obtain adduct, then adduct changes into polyaddition products, prepares super branched polyurethane.But these super branched polyurethanes all can not solidify by fast light.
In recent years, in succession have the preparation of ultra-branched polyurethane acrylate that can UV photocuring, Zeng Xingrong etc., with the monomer modified hyperbranched aliphatic polyester of homemade vulcabond-hydroxyethyl methylacrylate, prepare ultra-branched polyurethane acrylate; Xie Hui etc. prepare superbrnaching end-hydroxy polyester with TriMethylolPropane(TMP) and phthalic anhydride, then ester modified to hyperbranched poly with homemade vulcabond-Propylene glycol monoacrylate monomer, prepare ultra-branched polyurethane acrylate; Above synthesizing is all with the homemade urethane monomer modified ultra-branching polyester containing acrylic double bond.Shi Wenfang etc. prepare super branched polyurethane with the reaction of vulcabond and diethanolamine, then with homemade vulcabond-Hydroxyethyl acrylate monomer to super branched polyurethane modification, prepare ultra-branched polyurethane acrylate; Beam big waves etc. are prepared the super branched polyurethane coating of ultra-branched polyurethane acrylate and light/damp dual cure with similar method; This kind of method is with the homemade urethane monomer modified ultra-branching urethane containing acrylic double bond.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing ultra-branched polyurethane acrylate UV light-cured resin.Be exactly to prepare the ultra-branched polyurethane acrylate that simultaneously contains alkyl chain, amino-formate bond and acrylic double bond specifically, curable after UV rayed.Suitable separately or match with other common UV light-cured resin, be applied to the fields such as coating, sizing agent, auxiliary rheological agents of fast-photocurable, to meet the requirement that people are more and more higher to energy-conserving and environment-protective.There is not yet up to now the report that adopts ultra-branched polyurethane acrylate UV light-cured resin prepared by method therefor of the present invention.
Concrete technological method of the present invention is as follows:
1) diisocyanate monomer reacts in aprotic solvent with dibasic alcohol, and the reaction intermediate that obtains on average containing two isocyanate group (is called for short A
2);
2) make A
2react with mono amino poly-hydroxy monomer, the reaction intermediate that obtains on average containing an isocyanic ester and a plurality of hydroxyls (is called for short AB
n);
3) adjust reaction conditions, make AB
nmonomer generation self-condensation reaction, obtains on average containing the super branched polyurethane (HPU-X of 2-32 terminal hydroxy group
m);
4) diisocyanate monomer reacts in aprotic solvent with vinylformic acid hydroxyl ester monomer, obtains on average containing the reaction intermediate C of an isocyanic ester and an acrylic double bond;
5) HPU and reaction intermediate C are reacted in aprotic solvent, what obtain on average containing 2-32 end acrylic double bond can UV photocuring ultra-branched polyurethane acrylate resin (HPUA-X
m), this product separation, after dry, obtain white powder ultra-branched polyurethane acrylate UV cured resin solid phase prod.
This product is dissolved in solvent, curable after UV rayed.
Resulting ultra-branched polyurethane acrylate can be applied to produce the fields such as photocureable polymer, photo-cured coating, Photocurable adhesive, and as the purposes of thinner, auxiliary rheological agents, thixotropic agent, nucleator, active compound carriers or support of the catalyst, meet the requirement that people are more and more higher to energy-conserving and environment-protective, have broad application prospects.
Further describe by the following examples the preparation method of ultra-branched polyurethane acrylate UV light-cured resin of the present invention.But the present invention is not limited to listed example.
embodiment:
Embodiment 1:
Under 50 ℃ of stirrings, the mixed solution of 6.75g BDO (BDO) and 20g DMF (DMF) is added in 33.344g isophorone diisocyanate (IPDI), react 2 hours, obtain colourless transparent liquid; Reaction system is cooled to 0 ℃, the mixed solution of 7.89g diethanolamine (DEOA) and 20g DMF (DMF) is added in reaction system, react 3 hours, obtain colourless transparent liquid; Control reaction conditions, react end-blocking after 4.5 hours, separated, the dry white powder super branched polyurethane that obtains.
The mixed solution that adds 44.458g IPDI and 50g DMF under 50 ℃ of stirrings, constant pressure funnel drips 23.224 g HEA and 30g DMF solution, reacts half affixture that obtains IPDI/HEA for 4 hours.
Calculate remaining in super branched polyurethane-OH content, then with its equimolar amount, add IPDI/HEA, rising temperature to 45 ℃, reacts end-blocking after 3 hours, separated, the dry white powder ultra-branched polyurethane acrylate UV light-cured resin that obtains.
Embodiment 2:
26.123g tolylene diisocyanate (TDI) is dissolved in 30g DMF (DMF), under 45 ℃ of stirrings, adds 8.85g 1,6-hexylene glycol (HDO) and 10g N, the mixed solution of dinethylformamide (DMF), isothermal reaction 3 hours, obtains micro-yellow transparent liquid; System cooling temperature, to-10 ℃, is added to the mixed solution of 7.89g diethanolamine (DEOA) and 10g DMF (DMF) in reaction system, reacts 3 hours, obtain micro-yellow transparent liquid; Control reaction conditions, react end-blocking after 4 hours, separated, the dry white powder super branched polyurethane that obtains.
Under 40 ℃ of stirrings, add 33.344g IPDI and 50g DMF mixed solution, constant pressure funnel drips 17.418g HEA and 30g DMF solution, reacts half affixture that obtains IPDI/HEA for 4 hours.
Calculate remaining in super branched polyurethane-OH content, then with its equimolar amount, add IPDI/HEA, rising temperature to 45 ℃, reacts end-blocking after 3 hours, obtains white powder ultra-branched polyurethane acrylate UV light-cured resin after separated, dry.
Claims (10)
1. the preparation method of ultra-branched polyurethane acrylate UV light-cured resin, is characterized in that reaction undertaken by following several steps:
1) diisocyanate monomer reacts in aprotic solvent with dibasic alcohol, and the reaction intermediate that obtains on average containing two isocyanate group (is called for short A
2);
2) make A
2react with mono amino poly-hydroxy monomer, the reaction intermediate that obtains on average containing an isocyanic ester and a plurality of hydroxyls (is called for short AB
n);
3) adjust reaction conditions, make AB
nmonomer generation self-condensation reaction, obtains on average containing the super branched polyurethane (HPU-X of 2-32 terminal hydroxy group
m);
4) diisocyanate monomer reacts in aprotic solvent with vinylformic acid hydroxyl ester monomer, obtains on average containing the reaction intermediate C of an isocyanic ester and an acrylic double bond;
5) by HPU-X
mc reacts in aprotic solvent with reaction intermediate, and what obtain on average containing 2-32 end acrylic double bond can UV photocuring ultra-branched polyurethane acrylate resin (HPUA-X
m), this product separation, after dry, obtain white powder ultra-branched polyurethane acrylate UV cured resin solid phase prod.
2. the preparation method of ultra-branched polyurethane acrylate according to claim 1, is characterized in that making in step 1) diisocyanate monomer and diol reaction; Diisocyanate monomer used is for the compound that contains two isocyanate groups (N=C=O) or their mixture, comprising tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene diisocyanate etc.; Dibasic alcohol used is the end group alcohol compound that contains two hydroxyls or their mixture, comprising butyleneglycol, and hexylene glycol, polyoxyethylene glycol, polypropylene glycol, polyether Glycols, polyester diol etc.
3. the preparation method of ultra-branched polyurethane acrylate according to claim 1, is characterized in that step 2) in make A
2intermediate and mono amino poly-hydroxy monomer reaction; Mono amino poly-hydroxy monomer used is for to contain an amino and the compound of two (or more than two) hydroxyls or their mixture, comprising diethanolamine, diisopropanolamine (DIPA), tri methylol amino methane, GalN etc.
4. the preparation method of ultra-branched polyurethane acrylate according to claim 1, is characterized in that making in step 3) AB
2monomer generation self-condensation reaction is prepared super branched polyurethane (HPU-X
m).
5. the preparation method of ultra-branched polyurethane acrylate according to claim 1, is characterized in that making in step 4) diisocyanate monomer and vinylformic acid hydroxyl ester monomer reaction preparation feedback intermediate C; Vinylformic acid hydroxyl ester used is the compound that contains a hydroxyl and an acrylic double bond or their mixture, comprising Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester etc.
6. the preparation method of ultra-branched polyurethane acrylate according to claim 1, is characterized in that making in step 5) HPU-X
mreact and prepare HPUA-X with reaction intermediate C
m.
7. the preparation method of ultra-branched polyurethane acrylate according to claim 1, it is characterized in that step 1) temperature of reaction is-20～60 ℃, reaction times is 1 minute～72 hours, the reinforced mol ratio > 1.1/1 between diisocyanate monomer used and dibasic alcohol; Step 2) temperature of reaction is-20～60 ℃, and the reaction times is 1 minute～48 hours, A used
2reinforced mol ratio between intermediate and mono amino poly-hydroxy monomer is 1/20～20/1; Step 3) temperature of reaction is 0～60 ℃, and the reaction times is 10 minutes～96 hours; Step 4) temperature of reaction is-20～60 ℃, and the reaction times is 1 minute～48 hours, and the reinforced mol ratio between vulcabond used and acrylate is about 1/1; Step 5) temperature of reaction is 0～60 ℃, and the reaction times is 10 minutes～96 hours, HPU-X used
mwith the reinforced mol ratio of reaction intermediate C be 1/32～1/2.
8. the preparation method of ultra-branched polyurethane acrylate according to claim 1, it is characterized in that aprotic solvent is single aprotic solvent or the mixed solvent that contains multiple aprotic solvent, comprising dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, chloroform, tetrahydrofuran (THF), ethyl acetate and butylacetate etc.
9. the preparation method of ultra-branched polyurethane acrylate according to claim 1, is characterized in that adopting method used in claim 1～8 to obtain ultra-branched polyurethane acrylate light-cured resin HPUA-X
m, after separated, dry, obtain white powder ultra-branched polyurethane acrylate solid phase prod.
10. ultra-branched polyurethane acrylate according to claim 1 can be used as and produces that UV cure polymer, UV are coating material solidified, the purposes of the component of UV cure adhesive, and as the purposes of phase expanding material, thinner, rheological agent, thixotropic agent, active compound carriers.
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| CN201310667832.4A CN103709373B (en) | 2013-12-11 | 2013-12-11 | Ultra-branched polyurethane acrylate UV light-cured resin and preparation method thereof |
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| CN201310667832.4A CN103709373B (en) | 2013-12-11 | 2013-12-11 | Ultra-branched polyurethane acrylate UV light-cured resin and preparation method thereof |
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| CN103709373B CN103709373B (en) | 2018-11-27 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231214A (en) * | 2014-08-22 | 2014-12-24 | 江门职业技术学院 | Preparation method of cored UV-curable hyperbranched polyurethane acrylate resin |
| CN107400407A (en) * | 2017-08-16 | 2017-11-28 | 中山市中益油墨涂料有限公司 | The LED light cured printing ink of environment-friendly energy-saving and its application |
| CN107903372A (en) * | 2017-10-20 | 2018-04-13 | 广东工业大学 | A kind of UV photocurings flexibility ultra-branched polyurethane acrylate resin and preparation method and application |
| CN108383975A (en) * | 2018-02-27 | 2018-08-10 | 华南理工大学 | A kind of preparation method of antibacterial polypeptide modification polyurethane nano film |
| CN108641060A (en) * | 2018-04-28 | 2018-10-12 | 华南理工大学 | Cure vinyl ultra-branching polyurethane and preparation method thereof for UV-LED |
| CN108641064A (en) * | 2018-04-28 | 2018-10-12 | 华南理工大学 | Cure vinyl ultra-branching aqueous polyurethane and its synthetic method for UV-LED |
| CN109851751A (en) * | 2018-12-13 | 2019-06-07 | 江门市制漆厂有限公司 | Radiation-curable/damp solidified resin of a kind of Diamond Search and preparation method thereof |
| CN111534267A (en) * | 2020-04-15 | 2020-08-14 | 广州回天新材料有限公司 | Ultraviolet light curing adhesive and preparation method and application thereof |
| CN112515289A (en) * | 2020-11-20 | 2021-03-19 | 福建晋江市光宇鞋模有限公司 | Novel sole and sole manufacturing method |
| CN114149565A (en) * | 2021-11-30 | 2022-03-08 | 江苏三木化工股份有限公司 | Preparation method of light-curable hyperbranched polyurethane-epoxy acrylate |
| CN114213963A (en) * | 2021-12-31 | 2022-03-22 | 武汉中科先进技术研究院有限公司 | Photo-thermal dual-curing solvent-free wear-resistant antifogging coating and preparation method and application thereof |
| CN114230765A (en) * | 2021-12-17 | 2022-03-25 | 江南大学 | Preparation method of polyurea with anti-corrosion performance of micro-arc oxidation surface enhanced through UV curing |
| CN114958089A (en) * | 2022-05-19 | 2022-08-30 | 广东阿诺捷喷墨科技有限公司 | Wear-resistant UV ink for tape measure, preparation method and tape measure |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231214A (en) * | 2014-08-22 | 2014-12-24 | 江门职业技术学院 | Preparation method of cored UV-curable hyperbranched polyurethane acrylate resin |
| CN107400407A (en) * | 2017-08-16 | 2017-11-28 | 中山市中益油墨涂料有限公司 | The LED light cured printing ink of environment-friendly energy-saving and its application |
| CN107400407B (en) * | 2017-08-16 | 2020-06-30 | 中山市中益油墨涂料有限公司 | Environment-friendly energy-saving LED (light-emitting diode) photocuring ink and application thereof |
| CN107903372A (en) * | 2017-10-20 | 2018-04-13 | 广东工业大学 | A kind of UV photocurings flexibility ultra-branched polyurethane acrylate resin and preparation method and application |
| CN108383975A (en) * | 2018-02-27 | 2018-08-10 | 华南理工大学 | A kind of preparation method of antibacterial polypeptide modification polyurethane nano film |
| CN108641060A (en) * | 2018-04-28 | 2018-10-12 | 华南理工大学 | Cure vinyl ultra-branching polyurethane and preparation method thereof for UV-LED |
| CN108641064A (en) * | 2018-04-28 | 2018-10-12 | 华南理工大学 | Cure vinyl ultra-branching aqueous polyurethane and its synthetic method for UV-LED |
| CN109851751B (en) * | 2018-12-13 | 2021-01-15 | 江门市制漆厂有限公司 | zero-VOC (volatile organic compound) radiation curing/moisture curing resin and preparation method thereof |
| CN109851751A (en) * | 2018-12-13 | 2019-06-07 | 江门市制漆厂有限公司 | Radiation-curable/damp solidified resin of a kind of Diamond Search and preparation method thereof |
| CN111534267A (en) * | 2020-04-15 | 2020-08-14 | 广州回天新材料有限公司 | Ultraviolet light curing adhesive and preparation method and application thereof |
| CN112515289A (en) * | 2020-11-20 | 2021-03-19 | 福建晋江市光宇鞋模有限公司 | Novel sole and sole manufacturing method |
| CN114149565A (en) * | 2021-11-30 | 2022-03-08 | 江苏三木化工股份有限公司 | Preparation method of light-curable hyperbranched polyurethane-epoxy acrylate |
| CN114149565B (en) * | 2021-11-30 | 2023-04-25 | 江苏三木化工股份有限公司 | Preparation method of photo-curable hyperbranched polyurethane-epoxy acrylate |
| CN114230765A (en) * | 2021-12-17 | 2022-03-25 | 江南大学 | Preparation method of polyurea with anti-corrosion performance of micro-arc oxidation surface enhanced through UV curing |
| CN114213963A (en) * | 2021-12-31 | 2022-03-22 | 武汉中科先进技术研究院有限公司 | Photo-thermal dual-curing solvent-free wear-resistant antifogging coating and preparation method and application thereof |
| CN114958089A (en) * | 2022-05-19 | 2022-08-30 | 广东阿诺捷喷墨科技有限公司 | Wear-resistant UV ink for tape measure, preparation method and tape measure |
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